U.S. patent number 5,733,693 [Application Number 08/777,996] was granted by the patent office on 1998-03-31 for method for improving the readability of data processing forms.
This patent grant is currently assigned to Kimberly-Clark Worldwide, Inc.. Invention is credited to John Gavin MacDonald, Michael Wilfred Mosehauer, Ronald Sinclair Nohr.
United States Patent |
5,733,693 |
Nohr , et al. |
March 31, 1998 |
Method for improving the readability of data processing forms
Abstract
A data processing form for use with photo-sensing apparatus that
detect the presence of indicia at indicia-receiving locations on
the form. The form is composed of a sheet of carrier material and
plurality of indicia-receiving locations. The indicia-receiving
locations are defined by a mutable colored composition including a
mutable colorant and an ultraviolet radiation transorber such that
the indicia-receiving locations are adapted to become substantially
undetectable by photo-sensing apparatus upon irradiating the
colored composition with ultraviolet radiation at a dosage level
sufficient to irreversibly mutate the colorant. The colored
composition may be irradiated with radiation in the ultraviolet
region of the ultraviolet spectrum. Also disclosed is a data
processing form that includes a plurality of mutable indicia, at
least a portion of which are adapted to become substantially
undetectable by photo-sensing apparatus upon irradiation with an
effective dosage level of ultraviolet radiation such as, for
example, ultraviolet radiation. One embodiment of the present
invention encompasses a method for improving the readability of a
data processing form used in photo-sensing apparatus. Another
embodiment of the present invention encompasses a method of
modifying indicia on a data processing form used in photo-sensing
apparatus.
Inventors: |
Nohr; Ronald Sinclair
(Rosewell, GA), MacDonald; John Gavin (Decatur, GA),
Mosehauer; Michael Wilfred (Rochester, NY) |
Assignee: |
Kimberly-Clark Worldwide, Inc.
(Neenah, WI)
|
Family
ID: |
27537065 |
Appl.
No.: |
08/777,996 |
Filed: |
January 2, 1997 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
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453912 |
May 30, 1995 |
|
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360501 |
Dec 21, 1994 |
|
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|
258858 |
Jun 13, 1994 |
|
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|
119912 |
Sep 10, 1993 |
|
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|
103503 |
Aug 5, 1993 |
|
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Current U.S.
Class: |
430/21; 347/264;
430/19 |
Current CPC
Class: |
B41M
3/14 (20130101); B41M 5/26 (20130101); B41M
5/284 (20130101); B41M 5/46 (20130101); B43M
11/08 (20130101); C07C 65/38 (20130101); C07C
69/76 (20130101); C08B 37/0012 (20130101); C08B
37/0015 (20130101); C09B 67/0071 (20130101); C09D
11/17 (20130101); C09D 11/30 (20130101); C09D
11/36 (20130101); G03G 9/08 (20130101); G03G
9/0825 (20130101); G03G 9/08777 (20130101); G03G
9/0906 (20130101); G03G 9/0926 (20130101); G03G
9/09708 (20130101); G03G 9/09733 (20130101); G03G
9/09741 (20130101); G03G 9/0975 (20130101); G03G
9/09758 (20130101); G03G 9/09775 (20130101); G03G
9/09791 (20130101); G06K 1/121 (20130101); G06K
19/06046 (20130101) |
Current International
Class: |
B43M
11/08 (20060101); B43M 11/00 (20060101); B41M
5/28 (20060101); B41M 5/46 (20060101); B41M
5/26 (20060101); B41M 5/40 (20060101); B41M
3/14 (20060101); C07C 65/38 (20060101); C07C
65/00 (20060101); C08B 37/00 (20060101); C07C
69/00 (20060101); C07C 69/76 (20060101); C08B
37/16 (20060101); C09B 67/00 (20060101); C09D
11/00 (20060101); C09D 11/16 (20060101); C09B
67/42 (20060101); G03G 9/09 (20060101); G03G
9/08 (20060101); G03G 9/087 (20060101); G03G
9/097 (20060101); G09C 5/00 (20060101); G06K
1/12 (20060101); G06K 19/06 (20060101); G06K
1/00 (20060101); G03C 011/00 () |
Field of
Search: |
;430/19,21 ;203/85
;346/21 ;106/2A,21A,22B ;434/363 ;347/264 |
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|
Primary Examiner: McPherson; John A.
Attorney, Agent or Firm: Jones & Askew
Parent Case Text
CROSS-REFERENCE TO RELATED APPLICATION
This application is a continuation of U.S. application Ser. No.
08/453,912, filed May 30, 1995, now abandoned, which is a division
of U.S. application Ser. No. 08/360,501, filed on Dec. 21, 1994,
now allowed, which is a continuation-in-part of U.S. application
Ser. No. 08/258,858, filed on Jun. 13, 1994, now abandoned, which
is a continuation-in-part of U.S. application Ser. No. 08/119,912,
filed Sept. 10, 1993, now abandoned, which is a
continuation-in-part of U.S. application Ser. No. 08/103,503, filed
on Aug. 5, 1993, now abandoned.
Claims
What is claimed is:
1. A method for improving the readability of a data processing form
used in photo-sensing apparatus that detect the presence of indicia
at indicia-receiving locations on the form, the method
comprising:
providing a data processing form that includes a sheet of carrier
material and indicia located in a plurality of indicia-receiving
locations on at least a first surface of the sheet, the
indicia-receiving locations being defined by a mutable colored
composition comprising a mutable colorant and an ultraviolet
radiation transorber;
irradiating the colored composition with ultraviolet radiation at a
dosage level sufficient to irreversibly mutate the colorant so that
the indicia-receiving locations are substantially undetectable by
photo-sensing apparatus, leaving the indicia to be detected;
and
reading the form in a photo-sensing apparatus.
2. The method of claim 1, wherein the colored composition is
irradiated with ultraviolet radiation at a wavelength of from about
100 to about 375 nanometers.
3. The method of claim 2, wherein the ultraviolet radiation is
incoherent, pulsed ultraviolet radiation from a dielectric barrier
discharge excimer lamp.
4. The method of claim 1, wherein the data processing form is a
transmitted-read data processing form.
5. The method of claim 1, wherein the data processing form is a
reflective-read data processing form.
6. The method of claim 1, wherein the carrier material is
substantially opaque.
7. The method of claim 1, wherein the carrier material is
substantially translucent.
8. The method of claim 1, wherein the indicia-receiving locations
are defined by a mutable colored composition further comprising a
molecular includant.
9. The method of claim 8, wherein the molecular includant is
selected from the group consisting of clathrates, zeolites and
cyclodextrins.
10. The method of claim 8, wherein the mutable colorant and the
ultraviolet radiation transorber are associated with the molecular
includant.
11. A method of modifying indicia on a data processing form used in
photo-sensing apparatus that detect the presence of indicia at
indicia-receiving locations on the form, the method comprising:
providing a data processing form that includes a sheet of carrier
material and a plurality of indicia located at indicia-receiving
locations on at least a first surface of the sheet, at least a
portion of the indicia being mutable indicia formed from a colored
composition comprising a mutable colorant and an ultraviolet
radiation transorber;
reading the form in a photo-sensing apparatus; and
irradiating the colored composition with ultraviolet radiation at a
dosage level sufficient to irreversibly mutate the colorant so that
the mutable indicia are substantially undetectable by photo-sensing
apparatus.
12. The method of claim 11, wherein the colored composition is
irradiated with ultraviolet radiation at a wavelength of from about
100 to about 375 nanometers.
13. The method of claim 12, wherein the ultraviolet radiation is
incoherent, pulsed ultraviolet radiation from a dielectric barrier
discharge excimer lamp.
14. The method of claim 11, wherein the data processing form is a
transmitted-read data processing form.
15. The method of claim 11, wherein the data processing form is a
reflective-read data processing form.
16. The method of claim 11, wherein the carrier material is
substantially opaque.
17. The method of claim 11, wherein the carrier material is
substantially translucent.
18. The method of claim 11, wherein at least a portion of the
indicia are formed from a mutable colored composition further
comprising a molecular includant.
19. The method of claim 18, wherein the molecular includant is
selected from the group consisting of clathrates, zeolites and
cyclodextrins.
20. The method of claim 18, wherein the mutable colorant and the
ultraviolet radiation transorber are associated with the molecular
includant.
21. The method of claim 11, further comprising reading the form in
a photo-sensing apparatus after irradiating the colored
composition.
22. A method of modifying indicia on a data processing form used in
photo-sensing apparatus that detect the presence of indicia at
indicia-receiving locations on the form, the method comprising:
providing a data processing form that includes a sheet of carrier
material and a plurality of indicia located at indicia-receiving
locations on at least a first surface of the sheet, at least a
portion of the indicia being mutable indicia formed from a colored
composition comprising a mutable colorant and an ultraviolet
radiation transorber;
irradiating the colored composition with ultraviolet radiation at a
dosage level sufficient to irreversibly mutate the colorant so that
the mutable indicia are substantially undetectable by photo-sensing
apparatus; and
reading the form in a photo-sensing apparatus.
23. The method of claim 22, wherein the colored composition is
irradiated with ultraviolet radiation at a wavelength of from about
100 to about 375 nanometers.
24. The method of claim 23, wherein the ultraviolet radiation is
incoherent, pulsed ultraviolet radiation from a dielectric barrier
discharge excimer lamp.
25. The method of claim 22, wherein the data processing form is a
transmitted-read data processing form.
26. The method of claim 22, wherein the data processing form is a
reflective-read data processing form.
27. The method of claim 22, wherein the carrier material is
substantially opaque.
28. The method of claim 22, wherein the carrier material is
substantially translucent.
29. The method of claim 22, wherein at least a portion of the
indicia are formed from a mutable colored composition further
comprising a molecular includant.
30. The method of claim 29, wherein the molecular includant is
selected from the group consisting of clathrates, zeolites, and
cyclodextrins.
31. The method of claim 29, wherein the mutable colorant and the
ultraviolet radiation transorber are associated with the molecular
includant.
Description
TECHNICAL FIELD
The present invention relates generally to the field of optically
scanned documents. More particularly, the present invention relates
to a data processing document of the type used with photo-sensing
apparatus that detect the presence of indicia at indicia-receiving
locations on the document.
BACKGROUND OF THE INVENTION
Optical or conductive mark scanning systems of several types used
to read and record large amounts of data very quickly are well
known in the prior art. Such systems are typically used to process
data from documents such as, for example, sheets of paper, cards,
labels, tags, or other material. Generally speaking, some types of
these documents have a plurality of pre-printed control marks
(sometimes called "timing marks") in a control mark column
(sometimes called a "timing track") used to trigger the system to
scan or "read" certain data marks (also called "indicia") or data
response areas (also called "indicia-receiving locations"). The
data response areas are placed in a specified relation to the
control marks. Usually, a firmware programmable read only memory
(PROM) or software template and data processing means are used to
keep track of control marks and data marks. The processing means
will normally be programmed to work with a specific document format
(e.g., it will expect a certain number of control marks and a
certain pattern of data response areas in relation to the control
marks).
At least two distinct optical scanning methods are used to detect
the presence of indicia (e.g., data marks), control marks or other
marks in data response areas (i.e., indicia-receiving locations).
In one method, a light source placed at one surface of a document
illuminates the area to be read and a photo-sensor placed at the
opposite surface of the document is used to sense light that is
transmitted through the document. The photo-sensor detects
differences between the levels of light transmitted through marked
and unmarked areas.
In another method, both the light source and the photosensor are
located on the same side of the document that is scanned. The
photo-sensor detects differences between the levels of light
reflected by marked and unmarked areas when they are illuminated.
In both methods, the output of the photo-sensor is processed
electronically to determine the presence or absence of a mark.
Both methods have limitations that may affect the ability of a
photo-sensing apparatus to accurately detect the information on
data processing forms. One limitation is related to the placement
of indicia (e.g., data marks) in the data response areas (i.e.,
indicia-receiving locations). Each indicia-receiving location may
be outlined or otherwise designated by some sort of marking printed
on certain types of data processing forms. In some embodiments,
indicia is placed in the indicia-receiving locations by darkening
the designated area or by printing or writing a response in
alpha-numeric characters or other such characters as may be
required.
Inaccurate responses may be generated by the photo-sensing
apparatus if the markings that designate the indicia-receiving
location interfere with the proper detection of indicia. As an
example, scannable answer sheets, census forms and the like are
filled-out by providing indicia within designated indicia-receiving
locations. If the indicia overlap any markings used to designate
the indicia-receiving locations, they might be improperly read by
the photo-sensor.
Conventional photo-sensing apparatus, which may incorporate
computer software and/or hardware, are often configured to inspect
or "look" precisely at areas designated to contain indicia and not
at other areas in order to discriminate between indicia (e.g., data
marks), stray indicia (e.g., stray data marks), non-indicia (e.g.,
material not intended to be detected by photo-sensing apparatus),
smudges, flaws in the document, or the like. Moreover, data
processing forms may have applications where only a few
indicia-receiving locations are expected to contain indicia. In
those situations, photo-sensing apparatus can be designed or
programmed to ignore indicia sensed in other areas. It is important
that the data processing form be as free of clutter or markings
which may interfere with the processing in order to simplify the
design of the photo-sensing apparatus and to enhance the accuracy
of processing. Accordingly, it is very desirable to eliminate or
otherwise render undetectable any text, graphics, position markers
(e.g., marks defining indicia-receiving locations), or other
markings that should not be detected by the photo-sensing apparatus
prior to processing.
Another limitation of conventional data processing form relates to
the indicia. In many situations, it may be desirable to quickly and
efficiently erase or modify the indicia that are to be detected by
photo-sensing apparatus. For example, data processing forms
containing indicia (e.g., dots, shapes, alpha-numeric characters,
lines, bars or the like) in formats, such as, for example, coupons,
packaging labels, parts labels, bar code labels or tags,
assembly-line work-in-progress labels or tags, or other items are
used in such large numbers that the cost of reprinting or replacing
the forms on each item simply to modify the indicia could become
significant.
Accordingly, there is a need for a data processing form that can be
used with a photo-sensing apparatus without the problem of indicia
overlapping the markings used to designate indicia-receiving
locations. There is also a need for a data processing form that
permits quick and efficient erasure or modification of the indicia
that are to be detected by photo-sensing apparatus.
SUMMARY OF THE INVENTION
The present invention addresses the needs described above by
providing, in one embodiment, a data processing form for use with
photo-sensing apparatus that detect the presence of indicia at
indicia-receiving locations on the form. Generally speaking, the
data processing form is composed of: 1) a sheet of carrier
material; and 2) a plurality of indicia-receiving locations on at
least a first surface of the sheet. The indicia-receiving locations
are defined by a colored composition including a mutable colorant
and an ultraviolet radiation transorber. When the colored
composition is irradiated with ultraviolet radiation at a dosage
level sufficient to irreversibly mutate the colorant, the
indicia-receiving locations are adapted to become substantially
undetectable by photo-sensing apparatus. Desirably, the colored
composition is irradiated with radiation in the ultraviolet region
of the electromagnetic spectrum having a wavelength range between
approximately 100 to 375 nanometers.
The present invention also relates to a data processing form that
includes a plurality of mutable indicia. At least a portion of the
indicia are formed from a colored composition including a mutable
colorant and an ultraviolet radiation transorber so that the
indicia are adapted to become substantially undetectable by
photo-sensing apparatus upon irradiation with an effective dosage
level of ultraviolet radiation.
According to the invention, the data processing form may include
text or graphics formed from the colored composition that includes
a mutable colorant and an ultraviolet radiation transorber.
The data processing form may be configured in any conventional
format. For example, the data processing form may be a
transmitted-read form or a reflective-read form. The carrier
material component of the data processing form may be substantially
opaque, substantially translucent or substantially transparent.
The colored composition used in the data processing form of the
present invention includes a colorant and an ultraviolet radiation
transorber. The colorant, in the presence of the ultraviolet
radiation transorber, is adapted, upon exposure of the transorber
to ultraviolet radiation, to be mutable. The ultraviolet radiation
transorber is adapted to absorb ultraviolet radiation and interact
with the colorant to effect the irreversible mutation of the
colorant. It is desirable that the ultraviolet radiation transorber
absorb ultraviolet radiation at a wavelength of from about 4 to
about 400 nanometers. It is even more desirable that the
ultraviolet radiation transorber absorb ultraviolet radiation at a
wavelength of 100 to 375 nanometers.
The colored composition which includes a colorant and an
ultraviolet radiation transorber may also contain a molecular
includant having a chemical structure which defines at least one
cavity. The molecular includants include, but are not limited to,
clathrates, zeolites, and cyclodextrins. Each of the colorant and
ultraviolet radiation transorber is associated with one or more
molecular includants. For example, the colorant may be at least
partially included within a cavity of the molecular includant and
the ultraviolet radiation transorber may be associated with the
molecular includant outside of the cavity. As another example, the
ultraviolet radiation transorber may be covalently coupled to the
outside of the molecular includant.
The present invention encompasses a method for improving the
readability of a data processing form used in photo-sensing
apparatus. In general, the method includes the step of providing a
data processing form that includes a sheet of carrier material and
indicia located at a plurality of indicia-receiving locations on at
least a first surface of the sheet. At least a portion of the
indicia-receiving locations are defined by a mutable colored
composition including a mutable colorant and an ultraviolet
radiation transorber. Next, the colored composition is irradiated
with ultraviolet radiation at a dosage level sufficient to
irreversibly mutate the colorant so that the indicia-receiving
locations are substantially undetectable by photo-sensing
apparatus, leaving the indicia to be detected.
The present invention also encompasses a method of modifying
indicia on a data processing form used in photo-sensing apparatus.
In general, the method includes that step of providing a data
processing form that includes a sheet of carrier material and a
plurality of indicia at indicia-receiving locations on at least a
first surface of the sheet. At least a portion of the indicia are
mutable indicia formed from a colored composition comprising a
mutable colorant and an ultraviolet radiation transorber. Next, the
colored composition is irradiated with ultraviolet radiation at a
dosage level sufficient to irreversibly mutate the colorant so that
at least a portion of the mutable indicia are substantially
undetectable by photo-sensing apparatus.
Desirably, the colored composition is irradiated with radiation in
the ultraviolet region of the electromagnetic spectrum at a
wavelength of from about 100 to about 375 nanometers. In some
embodiments of the invention, it is desirable that the ultraviolet
radiation is incoherent, pulsed ultraviolet radiation from a
dielectric barrier discharge excimer lamp.
These and other objects, features and advantages of the present
invention will become apparent after a review of the following
detailed description of the disclosed embodiments and the appended
claims.
BRIEF DESCRIPTION OF THE FIGURES
FIG. 1 illustrates an ultraviolet radiation transorber/mutable
colorant/ molecular includant complex wherein the mutable colorant
is malachite green, the ultraviolet radiation transorber is
Irgacure 184 (1-hydroxycyclohexyl phenyl ketone), and the molecular
includant is .beta.-cyclodextrin.
FIG. 2 illustrates an ultraviolet radiation transorber/mutable
colorant/ molecular includant complex wherein the mutable colorant
is victoria pure blue BO (Basic Blue 7), the ultraviolet radiation
transorber is irgacure 184 (1-hydroxycyclohexyl phenyl ketone), and
the molecular includant is .beta.-cyclodextrin.
FIG. 3 is an illustration of several 222 nanometer excimer lamps
arranged in four parallel columns wherein the twelve numbers
represent the locations where twelve intensity measurements were
obtained approximately 5.5 centimeters from the excimer lamps.
FIG. 4 is an illustration of several 222 nanometer excimer lamps
arranged in four parallel columns wherein the nine numbers
represent the locations where nine intensity measurements were
obtained approximately 5.5 centimeters from the excimer lamps.
FIG. 5 is an illustration of several 222 nanometer excimer lamps
arranged in four parallel columns wherein the location of the
number "1" denotes the location where ten intensity measurements
were obtained from increasing distances from the lamps at that
location. (The measurements and their distances from the lamp are
summarized in Table 7.)
FIG. 6 is an illustration of an exemplary photo-sensing apparatus
based on the transmitted-read method.
FIG. 7 is an illustration of an exemplary photo-sensing apparatus
based on the reflective-read method.
FIG. 8 is an illustration of a portion of an exemplary data
processing form in which indicia-receiving locations are defined by
a mutable colored composition.
FIG. 9 is an illustration of a portion of an exemplary data
processing form depicted in FIG. 8 after the colorant in the
mutable colored composition has been irreversibly mutated.
FIG. 10 is an illustration of an exemplary data processing form in
which a portion of the indicia are formed from a mutable colored
composition.
FIG. 11 is an illustration of an exemplary data processing form
depicted in FIG. 10 after the colorant in the mutable colored
composition has been irreversibly mutated.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates in general to a data processing form
for use with photo-sensing apparatus that detect the presence of
indicia at indicia-receiving locations on the form.
The term "data processing form" and such variations including
"scannable form", "readable form", "scannable document" used herein
refer to a document, sheet, label, card, tag, sticker or the like
intended to hold information for detection by photo-sensing
apparatus. A data processing form may exist as an individual object
or it may be combined with or attached to items such as, for
example, containers, vehicles, parts, inventory, equipment,
packages and the like. Data processing forms can have many
applications, including but not limited to, answer sheets, census
forms, medical forms, identification cards, admission cards,
admission tickets, credit cards, monetary instruments, checks,
transportation tickets, coupons, bar code labels, bills, tags, or
the like.
As used herein, the term "indicia" refers to markings such as, for
example, dots, shapes, alpha-numeric characters, lines, bars or the
like that have sufficient size, contrast and/or intensity to be
detectable by photo-sensing apparatus.
As used herein, the term "indicia-receiving location" refers to a
discrete area of a data processing form that defines a space where
indicia may be placed for detection by photo-sensing apparatus.
Such an area may be single, plural, ordered or patterned and can be
referenced to control or reference marks used by a photo-sensing
apparatus. Inks, dyes and/or other materials may be used to
distinguish such an area from other areas of a data processing
form.
As used herein, the term "photo-sensing apparatus" refers to
conventional optical or conductive indicia (e.g., mark) scanning
systems used to read data from data processing forms. Generally
speaking, at least two distinct "photo-sensing" or optical scanning
methods are used to detect the presence of indicia or other marks
placed in response areas on data processing forms. In the
transmitted-read method, a light source placed at one surface of a
document illuminates an area to be read and a photo-sensor placed
at the opposite surface of the document is used to sense light that
is transmitted through the document at that area. When a mark is
present, generally little or no light is transmitted through the
document. In contrast, the absence of a mark means that significant
light will pass through the document. The transmitted light is
detected by the photo-sensor, and its output is processed by
electrical circuitry to determine the presence or absence of a
mark. Alternatively, and/or additionally, the wavelength or other
characteristics of the light may be modified by transmission
through indicia (e.g., marks) to create detectable differences.
Exemplary transmitted-read methods are disclosed in U.S. Pat. No.
4,114,028. In the reflective-read method, both the light source and
the photo-sensor are located on the same side of the document that
is scanned. The photo-sensor receives reflected light when an area
without a mark is illuminated. When a marked area is illuminated,
the light sensor receives little or no reflected light. Again, the
output of the photo-sensor is processed electronically to determine
the presence or absence of a mark. Alternatively, and/or
additionally, the wavelength or other characteristics of the light
may be modified by reflecting off indica (e.g., marks) to create
detectable differences. Systems using reflective-read methods are
disclosed by U.S. Pat. Nos. 3,676,690 and 4,300,123.
As used herein, the term "substantially undetectable" refers to a
state when indicia (or other markings such as, for example,
outlines of indicia-receiving locations) on a data processing form
that are detectable by a photo-sensing apparatus have been changed
sufficiently so they fail to provide the same detectable response
to transmitted or reflected light as unchanged indicia.
The term "composition" and such variations as "colored composition"
which are used herein with reference to a data processing form
refer to a colorant, and an ultraviolet radiation transorber. When
reference is being made to a colored composition which is adapted
for a specific application (e.g., a toner to be used in an
electrophotographic process or a printing fluid to be used in a
printing process employed in the preparation of the data processing
forms), the term "composition-based" is used as a modifier to
indicate that the material (e.g., a toner or a printing fluid)
includes a colorant, an ultraviolet radiation transorber, and,
optionally, a molecular includant.
As used herein, the term "colorant" is meant to include, without
limitation, any material which, in the presence of an ultraviolet
radiation transorber, is adapted upon exposure to ultraviolet
radiation to be mutable. It is contemplated that radiation at
wavelengths other than the ultraviolet region of the
electromagnetic spectrum may be used to effect such mutation. The
colorant typically will be an organic material, such as an organic
dye or pigment, including toners and lakes. Desirably, the colorant
will be substantially transparent to, i.e., will not significantly
interact with, the ultraviolet radiation or other effective
wavelength of electromagnetic radiation) to which it is exposed.
The term is meant to include a single material or a mixture of two
or more materials.
Organic dye classes include, by way of illustration only, triaryl
methyl dyes, such as Malachite Green Carbinol base
{4-(dimethylamino)-.alpha.-[4-(dimethylamino)phenyl]-.alpha.-phenyl-benzen
e-methanol}, Malachite Green Carbinol hydrochloride
{N-4-[[4(dimethylamino)phenyl]-phenylmethylene]-2,5-cyclohexadien-1-yliden
e]-N-methyl-methanaminium chloride or
bis[(p-dimethylamino)phenyl]phenylmethylium chloride}, and
Malachite Green oxalate
{N-4-[[4-(dimethylamino)phenyl]phenylmethylene]-2,5-cyclohexyldien-1-ylide
ne]-N-methylmethanaminium chloride or
bis[p-(dimethylamino)phenyl]phenylmethylium oxalate}, Victoria Pure
Blue BO
{N-[4-[[4-diethylamino)phenyl]-[4-(ethylamino)-1-naphthalenyl]methylene
]-2,5-cyclohexadien-1-yliden]-N-ethylethanaminium chloride}, and
Basic Fusion
{4-[(4-aminophenyl)-(4-imino-2,5-cyclohexadien-1-ylidene)methyl]-benzenami
ne monohydrochloride}; monoazo dyes, such as Cyanine Black,
Chrysoidine [Basic Orange 2; 4-(phenylazo)-1,3-benzenediamine
monohydrochloride], and .beta.-Naphthol Orange; thiazine dyes, such
as Methylene Green, zinc chloride double salt
[3,7-bis(dimethylamino)-6-nitrophenothiazin-5-ium chloride, zinc
chloride double salt]; oxazine dyes, such as Lumichrome
(7,8-dimethylalloxazine); naphthalimide dyes, such as Lucifer
Yellow CH
{6-amino-2-[(hydrazinocarbonyl)amino]-2,3-dihydro-1,3-dioxo-1H-benz[de]iso
quinoline-5,8-disulfonic acid dilithium salt}; azine dyes, such as
Janus Green B
{3-(diethylamino)-7-[[4-(dimethylamino)phenyl]azo]-5-phenylphenazinium
chloride}; cyanine dyes, such as Indocyanine Green {Cardio-Green or
Fox Green;
2-[7-[1,3-dihydro-1,1-dimethyl-3-(4-sulfobutyl)-2H-benz[e]indol-2-ylidene]
-1,3,5-heptatrienyl]-1,1-dimethyl-3-(4-sulfobutyl)-1H-benz[e]indolium
hydroxide inner salt sodium salt}; indigo dyes, such as Indigo
{Indigo Blue or Vat Blue 1;
2-(1,3-dihydro-3-oxo-2H-indol-2-ylidene)-1,2-dihydro-3H-indol-3-one};
coumarin dyes, such as 7-hydroxy-4-methylcoumarin (4-methylcoumarin
(4-methylumbelliferone); benzimidazole dyes, such as Hoechst 33258
[bisbenzimide or
2-(4-hydroxyphenyl)-5-(4-methyl-1-piperazinyl)-2,5-bi-1H-benzimidazole
trihydrochloride pentahydrate]; paraquinoidal dyes, such as
Hematoxylin {Natural Black 1;
7,11b-dihydrobenz[b]indeno[1,2-d]pyran-3,4,6a,9,10(6H)-pentol};
fluorescein dyes, such as Fluoresceinamine (5-aminofluorescein);
diazonium salt dyes, such as Diazo Red RC (Azoic Diazo No. 10 or
Fast Red RC salt; 2-methoxy-5-chlorobenzenediazonium chloride, zinc
chloride double salt); azoic diazo dyes, such as Fast Blue BB salt
(Azoic Diazo No. 20; 4-benzoylamino-2,5-diethoxybenzene diazonium
chloride, zinc chloride double salt); phenylenediamine dyes, such
as Disperse Yellow 9[N-(2,4-dinitrophenyl)-1,4-phenylenediamine or
Solvent Orange 53]; diazo dyes, such as Disperse Orange 13[Solvent
Orange 52; 1-phenylazo-4-(4-hydroxyphenylazo)naphthalene];
anthraquinone dyes, such as Disperse Blue 3[Celliton Fast Blue FFR;
1-methylamino-4-(2-hydroxyethylamino)-9,10-anthraquinone], Disperse
Blue 14 [Celliton Fast Blue B;
1,4-bis(methylamino)-9,10-anthraquinone], and Alizarin Blue Black B
(Mordant Black 13); trisazo dyes, such as Direct Blue 71 {Benzo
Light Blue FFL or Sirius Light Blue BRR;
3-[(4-[(4-[(6-amino-1-hydroxy-3-sulfo-2-naphthalenyl)azo]-6-sulfo-1naphtha
lenyl)azo]-1-naphthalenyl)azo]-1,5-naphthalenedisulfonic acid
tetrasodium salt}; xanthene dyes, such as 2,7-dichlorofluorescein;
proflavine dyes, such as 3,6-diaminoacridine hemisulfate
(Proflavine); sulfonaphthalein dyes, such as Cresol Red
(o-cresolsulfonaphthalein); phthalocyanine dyes, such as Copper
Phthalocyanine {Pigment Blue 15;
(SP-4-1)-[29H,31H-Phthalocyanato(2-)-N.sup.29,N.sup.30,N.sup.31,N.sup.32
]-copper}; carotenoid dyes, such as trans-.beta.-carotene (Food
Orange 5); carminic acid dyes, such as Carmine, the aluminum or
calcium-aluminum lake of carminic acid
(7-a-D-glucopyranosyl-9,10-dihydro-3,5,6,8-tetrahydroxy-1-methyl-9,10-diox
o-2-anthracenecarboxylic acid); azure dyes, such as Azure A
[3-amino-7-(dimethylamino)phenothiazin-5-ium chloride or
7-(dimethylamino)-3-imino-3H-phenothiazine hydrochloride]; and
acridine dyes, such as Acridine Orange [Basic Orange 14;
3,8-bis(dimethylamino)acridine hydrochloride, zinc chloride double
salt] and Acriflavine (Acriflavine neutral;
3,6-diamino-10-methylacridinium chloride mixture with
3,6-acridinediamine).
The term "mutable" with reference to the colorant is used to mean
that the absorption maximum of the colorant in the visible region
of the electromagnetic spectrum is capable of being mutated or
changed by exposure to ultraviolet radiation when in the presence
of the ultraviolet radiation transorber. Alternatively and/or
additionally, it is contemplated that radiation at wavelengths in
other regions of the electromagnetic spectrum may be used. In
general, it is only necessary that such absorption maximum be
mutated to an absorption maximum which is different from that of
the colorant prior to exposure to the ultraviolet radiation, and
that the mutation be irreversible. Thus, the new absorption maximum
can be within or outside of the visible region of the
electromagnetic spectrum. In other words, the colorant can mutate
to a different color or be rendered colorless, transparent, or
otherwise substantially undetectable by conventional photo-sensing
apparatus. The latter, of course, is desirable when the colorant is
used in a colored composition adapted to be utilized in the data
processing forms of the present invention.
As used herein, the term "irreversible" means that the colorant
will not revert to its original color when it no longer is exposed
to ultraviolet radiation (or radiation at other effective
wavelengths in the electromagnetic radiation spectrum). Desirably,
the mutated colorant will be stable, i.e., not appreciably
adversely affected by radiation normally encountered in the
environment, such as natural or artificial light and heat. Thus,
desirably, a colorant rendered colorless, transparent, or otherwise
substantially undetectable by conventional photo-sensing apparatus
will remain colorless or substantially undetectable
indefinitely.
The term "ultraviolet radiation transorber" is used herein to mean
any material which is adapted to absorb ultraviolet radiation (or
radiation at other effective wavelengths in the electromagnetic
radiation spectrum) and interact with the colorant to effect the
mutation of the colorant. In some embodiments, the ultraviolet
radiation transorber may be an organic compound. The term
"compound" is intended to include a single material or a mixture of
two or more materials. If two or more materials are employed, it is
not necessary that all of them absorb ultraviolet radiation of the
same wavelength. It is contemplated that the transorber may be
adapted to absorb radiation at other wavelengths
The data processing form of the present invention incorporates a
colored composition that includes unique compounds that are capable
of absorbing narrow ultraviolet wavelength radiation (or radiation
at other effective wavelengths in the electromagnetic radiation
spectrum). The compounds are synthesized by combining a
wavelength-selective sensitizer and a photoreactor. The
photoreactors oftentimes do not efficiently absorb high energy
radiation. When combined with wavelength-selective antennae that
correspond to the eximer lamp emission, the resulting compound is a
wavelength specific compound that efficiently absorbs a very narrow
spectrum of radiation. Examples of ultraviolet radiation
transorbers are shown in Examples 5 and 9 herein.
While the mechanism of the interaction of the ultraviolet radiation
transorber with the colorant is not totally understood, it is
believed that it may interact with the colorant in a variety of
ways. For example, the ultraviolet radiation transorber, upon
absorbing ultraviolet radiation, may be converted to one or more
free radicals which interact with the colorant. Such free
radical-generating compounds typically are hindered ketones, some
examples of which include, but are not limited to: benzildimethyl
ketal (available commercially as Irgacure.RTM. 651, Ciba-Geigy
Corporation, Hawthorne, N.Y.); 1hydroxycyclohexyl phenyl ketone
(Irgacure.RTM. 500);
2-methyl-1[4-(methylthio)phenyl]-2-morpholino-propan-1-one](Irgacure.RTM.
907); 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl )butan-1-one
(Irgacure.RTM. 369); and 1-hydroxycyclohexyl phenyl ketone
(Irgacure.RTM. 184).
Alternatively, the ultraviolet radiation may initiate an electron
transfer or reduction-oxidation reaction between the ultraviolet
radiation transorber and the colorant. In this case, the
ultraviolet radiation transorber may be, but is not limited to,
Michler's ketone (p-dimethylaminophenyl ketone) or benzyl trimethyl
stannate. Or, a cationic mechanism may be involved, in which case
the ultraviolet radiation transorber could be, for example,
bis[4-(diphenylsulphonio)phenyl)]sulfide bis-(hexafluorophosphate)
(Degacure.RTM. KI85, Ciba-Geigy Corporation, Hawthorne, N.Y.);
Cyracure.RTM. UVI-6990 (Ciba-Geigy Corporation), which is a mixture
of bis[4-(diphenylsulphonio)phenyl]sulfide bis(hexafluorophosphate)
with related monosulphonium hexafluorophosphate salts; and
5-2,4-(cyclopentadienyl)[1,2,3,4,5,6-(methylethyl)benzene]-iron-(II)
hexafluorophosphate (Irgacure.RTM. 261).
The term "ultraviolet radiation" is used herein to mean
electromagnetic radiation having wavelengths in the range of from
about 4 to about 400 nanometers. An especially desirable
ultraviolet radiation wavelength range is between approximately 100
to 375 nanometers. Thus, the term includes the regions commonly
referred to as ultraviolet and vacuum ultraviolet. The wavelength
ranges typically assigned to these two regions are from about 180
to about 400 nanometers and from about 100 to about 180 nanometers,
respectively.
In some embodiments, the molar ratio of ultraviolet radiation
transorber to colorant generally will be equal to or greater than
about 0.5. As a general rule, the more efficient the ultraviolet
radiation transorber is in absorbing the ultraviolet radiation and
interacting with, i.e., transferring absorbed energy to, the
colorant to effect irreversible mutation of the colorant, the lower
such ratio can be. Current theories of molecular photo chemistry
suggest that the lower limit to such ratio is 0.5, based on the
generation of two free radicals per photon. As a practical matter,
however, ratios higher than 1 are likely to be required, perhaps as
high as about 10. However, the colored compositions used with the
data processing form of the present invention are not bound by any
specific molar ratio range. The important feature is that the
transorber is present in an amount sufficient to effect mutation of
the colorant.
As a practical matter, the colorant, and ultraviolet radiation
transorber are likely to be solids. However, any or all of such
materials can be a liquid. In an embodiment where the colored
composition is a solid, the effectiveness of the ultraviolet
radiation transorber is improved when the colorant and ultraviolet
radiation transorber are in intimate contact. To this end, the
thorough blending of the two components, along with other
components which may be present, is desirable. Such blending
generally is accomplished by any of the means known to those having
ordinary skill in the art. When the colored composition includes a
polymer, blending is facilitated if the colorant and the
ultraviolet radiation transorber are at least partly soluble in
softened or molten polymer. In such case, the composition is
readily prepared in, for example, a two-roll mill. Alternatively,
the colored composition can be a liquid because one or more of its
components is a liquid.
For some applications, the colored composition typically will be
utilized in particulate form. In other applications, the particles
of the composition should be very small. For example, the particles
of a colored composition adapted for use as a toner in an
electrophotographic process that can be used to prepare the data
processing forms of the present invention may typically consist of
7-15 micrometer average diameter particles, although smaller or
larger particles can be employed. In such an application, the
particles should be as uniform in size as possible. Methods of
forming such particles are well known to those having ordinary
skill in the art.
Photochemical processes involve the absorption of light quanta, or
photons, by a molecule, e.g., the ultraviolet radiation transorber,
to produce a highly reactive electronically excited state. However,
the photon energy, which is proportional to the wavelength of the
radiation, cannot be absorbed by the molecule unless it matches the
energy difference between the unexcited, or original, state and an
excited state. Consequently, while the wavelength range of the
ultraviolet radiation to which the colored composition is exposed
is not directly of concern, at least a portion of the radiation
must have wavelengths which will provide the necessary energy to
raise the ultraviolet radiation transorber to an energy level which
is capable of interacting with the colorant.
It follows, then, that the absorption maximum of the ultraviolet
radiation transorber ideally will be matched with the wavelength
range of the ultraviolet radiation in order to increase the
efficiency of the mutation of the colorant. Such efficiency also
will be increased if the wavelength range of the ultraviolet
radiation is relatively narrow, with the maximum of the ultraviolet
radiation transorber coming within such range. For these reasons,
especially suitable ultraviolet radiation has a wavelength of from
about 100 to about 375 nanometers. Ultraviolet radiation within
this range desirably may be incoherent, pulsed ultraviolet
radiation from a dielectric barrier discharge excimer lamp.
The term "incoherent, pulsed ultraviolet radiation" has reference
to the radiation produced by a dielectric barrier discharge excimer
lamp (referred to hereinafter as "excimer lamp"). Such a lamp is
described, for example, by U. Kogelschatz, "Silent discharges for
the generation of ultraviolet and vacuum ultraviolet excimer
radiation," Pure & Appl. Chem., 62, No. 9, pp. 1667-1674
(1990); and E. Eliasson and U. Kogelschatz, "UV Excimer Radiation
from Dielectric-Barrier Discharges," Appl. Phys. B, 46, pp. 299-303
(1988). Excimer lamps were developed originally by ABB Infocom
Ltd., Lenzburg, Switzerland. The excimer lamp technology since has
been acquired by Harus Noblelight AG, Hanau, Germany.
The excimer lamp emits radiation having a very narrow bandwidth,
i.e., radiation in which the half width is of the order of 5-15
nanometers. This emitted radiation is incoherent and pulsed, the
frequency of the pulses being dependent upon the frequency of the
alternating current power supply which typically is in the range of
from about 20 to about 300 kHz. An excimer lamp typically is
identified or referred to by the wavelength at which the maximum
intensity of the radiation occurs, which convention is followed
throughout this specification. Thus, in comparison with most other
commercially useful sources of ultraviolet radiation which
typically emit over the entire ultraviolet spectrum and even into
the visible region, excimer lamp radiation is substantially
monochromatic.
Excimers are unstable molecular complexes which occur only under
extreme conditions, such as those temporarily existing in special
types of gas discharge. Typical examples are the molecular bonds
between two rare gaseous atoms or between a rare gas atom and a
halogen atom. Excimer complexes dissociate within less than a
microsecond and, while they are dissociating, release their binding
energy in the form of ultraviolet radiation. Known excimers, in
general, emit in the range of from about 125 to about 360
nanometers, depending upon the excimer gas mixture.
Although the colorant and the ultraviolet radiation transorber have
been described as separate compounds, they can be part of the same
molecule. For example, they can be covalently coupled to each
other, either directly, or indirectly through a relatively small
molecule, or spacer. Alternatively, the colorant and ultraviolet
radiation transorber can be covalently coupled to a large molecule,
such as an oligomer or a polymer, particularly when a solid colored
composition is desired. Further, the colorant and ultraviolet
radiation transorber may be associated with a large molecule by van
der Waals forces, and hydrogen bonding, among other means. Other
variations will be readily apparent to those having ordinary skill
in the art.
For example, the colored composition may also contain a molecular
includant. The term "molecular includant," as used herein, is
intended to mean any substance having a chemical structure which
defines at least one cavity. That is, the molecular includant is a
cavity-containing structure. As used herein, the term "cavity" is
meant to include any opening or space of a size sufficient to
accept at least a portion of one or both of the colorant and the
ultraviolet radiation transorber. Thus, the cavity can be a tunnel
through the molecular includant or a cave-like space in the
molecular includant. The cavity can be isolated or independent, or
connected to one or more other cavities.
The molecular includant can be inorganic or organic in nature. In
certain embodiments, the chemical structure of the molecular
includant is adapted to form a molecular inclusion complex.
Examples of molecular includants are, by way of illustration only,
clathrates or intercalates, zeolites, and cyclodextrins. Examples
of cyclodextrins include, but are not limited to,
alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin,
hydroxypropyl beta-cyclodextrin, hydroxyethyl beta-cyclodextrin,
sulfated beta-cyclodextrin, and sulfated gamma-cyclodextrin.
(American Maize-Products Company, of Hammond Ind.) In some
embodiments, the molecular includant is a cyclodextrin. More
particularly, in some embodiments, the molecular includant is an
alpha-cyclodextrin. In other embodiments, the molecular includant
is a beta-cyclodextrin. Although not wanting to be bound by the
following theory, it is believed that the closer the transorber
molecule is to the mutable colorant on the molecular includant, the
more efficient the interaction with the colorant to effect mutation
of the colorant. Thus, the molecular includant with functional
groups that can react with and bind the transorber molecule and
that are close to the binding site of the mutable colorant are the
more desirable molecular includants.
As used herein, the term "derivatized molecular includant" is used
herein to mean a molecular includant having more than two leaving
groups covalently coupled to each molecule of the molecular
includant. The term "leaving group" is used herein to mean any
leaving group capable of participating in a bimolecular
nucleophilic substitution reaction.
The colorant and the ultraviolet radiation transorber are
associated with the molecular includant. The term "associated" in
its broadest sense means that the colorant and the ultraviolet
radiation transorber are at least in close proximity to the
molecular includant. For example, the colorant and/or the
ultraviolet radiation transorber can be maintained in close
proximity to the molecular includant by hydrogen bonding, van der
Waals forces, or the like. Alternatively, either or both of the
colorant and the ultraviolet radiation transorber can be covalently
bonded to the molecular includant. In certain embodiments, the
colorant will be associated with the molecular includant by means
of hydrogen bonding and/or van der Waals forces or the like, while
the ultraviolet radiation transorber is covalently bonded to the
molecular includant. In other embodiments, the colorant is at least
partially included within the cavity of the molecular includant,
and the ultraviolet radiation transorber is located outside of the
cavity of the molecular includant. In one embodiment wherein the
colorant and the ultraviolet radiation transorber are associated
with the molecular includant, the colorant is crystal violet, the
ultraviolet radiation transorber is a dehydrated
phthaloylglycine-2959, and the molecular includant is
beta-cyclodextrin. In yet another embodiment wherein the colorant
and the ultraviolet radiation transorber are associated with the
molecular includant, the colorant is crystal violet, the
ultraviolet radiation transorber is 4(4-hydroxyphenyl)
butan-2-one-2959 (chloro substituted), and the molecular includant
is beta-cyclodextrin.
In another embodiment wherein the colorant and the ultraviolet
radiation transorber are associated with the molecular includant,
the colorant is malachite green, the ultraviolet radiation
transorber is Irgacure 184, and the molecular includant is
beta-cyclodextrin as shown in FIG. 1. In still another embodiment
wherein the colorant and the ultraviolet radiation transorber are
associated with the molecular includant, the colorant is victoria
pure blue BO, the ultraviolet radiation transorber is Irgacure 184,
and the molecular includant is beta-cyclodextrin as shown in FIG.
2.
Examples 5 through 9 disclose a method of preparing and associating
these colorants and ultraviolet radiation transorbers to
beta-cyclodextrins. It is to be understood that the methods
disclosed in Examples 5 through 9 are merely one way of preparing
and associating these components, and that many other methods known
in the chemical arts may be used. Other methods of preparing and
associated such components, or any of the other components which
may be used in the colored composition would be known to those of
ordinary skill in the art once the specific components have been
selected.
As a practical matter, the colorant, ultraviolet radiation
transorber, and molecular includant are likely to be solids.
However, any or all of such materials can be a liquid. The colored
composition can be a liquid either because one or more of its
components is a liquid, or, when the molecular includant is organic
in nature, a solvent is employed. Suitable solvents include, but
are not limited to, amides, such as N,N-dimethylformamide;
sulfoxides, such as dimethylsulfoxide; ketones, such as acetone,
methyl ethyl ketone, and methyl butyl ketone; aliphatic and
aromatic hydrocarbons, such as hexane, octane, benzene, toluene,
and the xylenes; esters, such as ethyl acetate; water; and the
like. When the molecular includant is a cyclodextrin, particularly
suitable solvents are the amides and sulfoxides.
The present invention also relates to a method of mutating the
colorant in the colored composition employed in the data processing
forms of the present invention. Briefly described, the method
includes the step of irradiating a composition containing a mutable
colorant and an ultraviolet radiation transorber with ultraviolet
radiation at a dosage level sufficient to mutate the colorant. As
stated above, the composition may include a molecular
includant.
The amount or dosage level of ultraviolet radiation that the
colorant is exposed to will generally be that amount which is
necessary to mutate the colorant. The amount of ultraviolet
radiation necessary to mutate the colorant can be determined by one
of ordinary skill in the art using routine experimentation. Power
density is the measure of the amount of radiated electromagnetic
power traversing a unit area and is usually expressed in watts per
centimeter squared (W/cm.sup.2). The power density level range is
between approximately 5 mW/cm.sup.2 and 15 mW/cm.sup.2, more
particularly 8 to 10 mW/cm.sup.2. The dosage level, in turn,
typically is a function of the time of exposure and the intensity
or flux of the radiation source which irradiates the colored
composition. The latter is effected by the distance of the
composition from the source and, depending upon the wavelength
range of the ultraviolet radiation, can be effected by the
atmosphere between the radiation source and the composition.
Accordingly, in some instances it may be appropriate to expose the
composition to the radiation in a controlled atmosphere or in a
vacuum, although in general neither approach is desired.
For example, in one embodiment, the colorant is mutated by exposure
to 222 nanometer excimer lamps. More particularly, the colorant
crystal violet is mutated by exposure to 222 nanometer lamps. Even
more particularly, the colorant crystal violet is mutated by
exposure to 222 nanometer excimer lamps located approximately 5 to
6 centimeters from the colorant, wherein the lamps are arranged in
four parallel columns approximately 30 centimeters long as shown in
FIGS. 3 and 4. It is to be understood that the arrangement of the
lamps is not critical to this aspect of the invention. Accordingly,
one or more lamps may be arranged in any configuration and at any
distance which results in the colorant mutating upon exposure to
the lamp's ultraviolet radiation. One of ordinary skill in the art
would be able to determine by routine experimentation which
configurations and which distances are appropriate. Also, it is to
be understood that different excimer lamps are to be used with
different ultraviolet radiation transorbers. The excimer lamp used
to mutate a colorant associated with an ultraviolet radiation
transorber should produce ultraviolet radiation of a wavelength
that is absorbed by the ultraviolet radiation transorber.
The colored composition can be utilized on or in any sheet of
carrier material (i.e., substrate used to make the data processing
form. It is important only that the colored composition form a
plurality of indicia or define a plurality of indicia-receiving
locations which generally appear to be "at about" or on at least a
first surface of the sheet. Accordingly, the expression "a
plurality of indicia-receiving locations on at least a surface of
the sheet" should be understood to encompass a plurality of
indicia-receiving locations which generally appear to be "at about"
or on at least a first surface of the sheet. Likewise, the
expression "a plurality of indicia at indicia-receiving locations
on at least a surface of the sheet" should be understood to
encompass a plurality of indicia at indicia-receiving locations,
both of which generally appear to be "at about" or on at least a
first surface of the sheet.
If the composition is present in the sheet of carrier material,
however, the carrier material should be substantially transparent
to the ultraviolet radiation which is employed to mutate the
colorant. That is, the ultraviolet radiation (or radiation at other
effective wavelengths in the electromagnetic radiation spectrum)
will not significantly interact with or be absorbed by the carrier
material. As a practical matter, the composition typically will be
placed on or incorporated into a sheet of carrier material, with
the most common carrier material being paper. Other carrier
materials, including, but not limited to, woven and nonwoven webs
or fabrics, films, cards, cardboard, or the like, can be used. It
is contemplated that the composition may be placed directly on
other items to be processed by photo-sensing apparatus, including
but not limited to, packaging, inventory, products, equipment,
machinery, parts, vehicles, collars, tags, containers, or the
like.
The data processing form of the present invention contains
indicia-receiving locations defined by the mutable colored
composition described herein. Alternatively and/or additionally,
the data processing form of the present invention may contain
indicia, text and/or graphics formed from the mutable colored
composition described herein. Although the data processing form of
the present invention may employ any sheet of carrier material
capable of having the colored composition fixed thereto or
incorporated therein, a desirable carrier material is paper.
Particular examples include, but are not limited to, photocopy
paper and facsimile paper.
By way of example, the colored composition can be incorporated into
a toner adapted to be utilized in an electrophotographic process
employed in the production of the data processing forms. The toner
includes the colorant, ultraviolet radiation transorber, and a
vehicle. The vehicle can be a polymer, and the toner may further
contain a charge control agent. Briefly described, the
electrophotographic process comprises the steps of creating an
image on a photoreceptor surface, applying toner to the
photoreceptor surface to form a toner image which replicates the
image, transferring the toner image to a substrate, and fixing the
toner image to the substrate. After the toner has been fixed on the
substrate, the colorant in the composition is mutated by
irradiating the substrate with ultraviolet radiation at a dosage
level sufficient to irreversibly mutate the colorant. In some
embodiments, the ultraviolet radiation used to mutate the colorant
will have wavelengths of from about 100 to about 375 nanometers. In
other embodiments, the ultraviolet radiation is incoherent, pulsed
ultraviolet radiation produced by a dielectric barrier discharge
excimer lamp. In another embodiment, the toner may further comprise
a molecular includant.
When the colored composition is adapted to be utilized as a toner
in an electrophotographic process (in the manufacture of the data
processing forms of the present invention), the composition also
will contain a vehicle, the nature of which is well known to those
having ordinary skill in the art. For many applications, the
carrier will be a polymer, typically a thermosetting or
thermoplastic polymer, with the latter being the more common.
Further examples of thermoplastic polymers include, but are not
limited to: end-capped polyacetals, such as poly(oxymethylene) or
polyformaldehyde, poly(trichloroacetaldehyde),
poly(n-valeraldehyde), poly(acetaldehyde), poly(propionaldehyde),
and the like; acrylic polymers, such as polyacrylamide,
poly(acrylic acid), poly(methacrylic acid), poly(ethyl acrylate),
poly(methyl methacrylate), and the like; fluorocarbon polymers,
such as poly(tetrafluoroethylene), perfluorinated ethylenepropylene
copolymers, ethylenetetrafluoroethylene copolymers,
poly(chlorotrifluoroethylene), ethylene-chlorotrifluoroethylene
copolymers, poly(vinylidene fluoride), poly(vinyl fluoride), and
the like; epoxy resins, such as the condensation products of
epichlorohydrin and bisphenol A; polyamides, such as
poly(6-aminocaproic acid) or poly(E-caprolactam),
poly(hexamethylene adipamide), poly(hexamethylene sebacamide),
poly(11-aminoundecanoic acid), and the like; polyaramides, such as
poly(imino-1,3-phenyleneiminoisophthaloyl) or poly(m-phenylene
isophthalamide), and the like; parylenes, such as poly-p-xylylene,
poly(chloro-p-xylene), and the like; polyaryl ethers, such as
poly(oxy-2,6-dimethyl-1,4-phenylene) or poly(p-phenylene oxide),
and the like; polyaryl sulfones, such as
poly(oxy-1,4-phenylenesulfonyl-1,4-phenyleneoxy-1,4-phenyleneisopropyliden
e-1,4-phenylene),
poly(sulfonyl-1,4-phenyleneoxy-1,4-phenylsenesulfonyl-4,4-biphenylene),
and the like; polycarbonates, such as poly(bisphenol A) or
poly(carbonyldioxy-1,4-phenylenelsopropylidene-1,4-phenylene), and
the like; polyesters, such as poly(ethylene terephthalate),
poly(tetramethylene terephthalate),
poly(cyclohexylene-1,4-dimethylene terephthalate) or
poly(oxymethylene-1,4-cyclohexylenemethyleneoxyterephthaloyl), and
the like; polyaryl sulfides, such as poly(p-phenylene sulfide) or
poly(thio-1,4-phenylene), and the like; polyimides, such as
poly-(pyromellitimido-1,4-phenylene), and the like; polyolefins,
such as polyethylene, polypropylene, poly(1-butene),
poly(2-butene), poly(1-pentene), poly(2-pentene),
poly(3-methyl-1pentene), poly(4-methyl-1-pentene),
1,2-poly-1,3-butadiene, 1,4-poly-1,3-butadiene, polyisoprene,
polychloroprene, polyacrylonitrile, poly(vinyl acetate),
poly(vinylidene chloride), polystyrene, and the like; and
copolymers of the foregoing, such as acrylonitrile-butadienestyrene
(ABS) copolymers, styrene-n-butylmethacrylate copolymers,
ethylenevinyl acetate copolymers, and the like.
Some of the more commonly used thermoplastic polymers include
styrene-n-butyl methacrylate copolymers, polystyrene,
styrene-n-butyl acryl ate copolymers, styrene-butadiene copolymers,
polycarbonates, poly(methyl methacrylate), poly(vinylidene
fluoride), polyamides (nylon-12), polyethylene, polypropylene,
ethylene-vinyl acetate copolymers, and epoxy resins.
Examples of thermosetting polymers include, but are not limited to,
alkyd resins, such as phthalic anhydride-glycerol resins, maleic
acid-glycerol resins, adipic acid-glycerol resins, and phthalic
anhydride-pentaerythritol resins; allylic resins, in which such
monomers as diallyl phthalate, diallyl isophthalate diallyl
maleate, and diallyl chlorendate serve as nonvolatile cross-linking
agents in polyester compounds; amino resins, such as
aniline-formaldehyde resins, ethylene urea-formaldehyde resins,
dicyandiamide-formaldehyde resins, melamine-formaldehyde resins,
sulfonamide-formaldehyde resins, and urea-formaldehyde resins;
epoxy resins, such as cross-linked epichlorohydrin-bisphenol A
resins; phenolic resins, such as phenol-formaldehyde resins,
including Novolacs and resols; and thermosetting polyesters,
silicones, and urethanes.
In addition to the colorant, and ultraviolet radiation transorber,
and optional vehicle, the colored composition may contain
additional components, depending upon the application for which it
is intended. For example, a composition which is to be utilized as
a toner in an electrophotographic process that may be used to make
the data processing forms of the present invention optionally can
contain, for example, charge control agents, stabilizers against
thermal oxidation, viscoelastic properties modifiers, cross-linking
agents, plasticizers, and the like. Further, a composition which is
to be utilized as a toner in an electrophotographic process
optionally can contain charge control additives such as a
quaternary ammonium salt; flow control additives such as
hydrophobic silica, zinc stearate, calcium stearate, lithium
stearate, polyvinylstearate, and polyethylene powders; and fillers
such as calcium carbonate, clay and talc, among other additives
used by those having ordinary skill in the art. For some
applications, the charge control agent will be the major component
of the toner. Charge control agents, of course, are well known to
those having ordinary skill in the art and typically are
polymer-coated metal particles. The identities and amounts of such
additional components in the colored composition are well known to
one of ordinary skill in the art. Further, the toner can also
incorporate a molecular includant as described above.
It should be understood from the discussion above that the colored
composition may be incorporated into printing fluids or other
materials used in printing processes, image-creating processes,
image-duplication processes or the like to generate indicia, marks,
text, graphics or the like and/or define indicia-receiving
locations "at about" or on at least one surface of a sheet of
carrier material to prepare the data processing forms of the
present invention.
Referring now to FIGS. 6 and 7, there is shown (not necessarily to
scale) an illustration of two exemplary methods for optical
scanning of the exemplary data processing forms addressed by the
present invention. In each method, portions of a data processing
form are sequentially scanned. This is usually accomplished by
transporting the data processing form through a scanning station
forming part of scanning equipment. Such equipment (not shown here)
usually includes a tray or other means for holding forms to be
scanned, transport means to pick up a single document at a time and
move it through the scanning station and an output tray or other
means for holding forms that have been scanned. As the form is
transported through the scanning station, one or more photo-sensing
apparatus is used to check for the presence or absence of indicia
(e.g., marks) in specified areas (i.e., indicia-receiving
locations). This photo-sensing apparatus generates electrical
signals that are processed to discriminate between the presence or
absence of a indicia. Data produced by the indicia discriminating
circuitry may be further processed by comparison to a control or
answer key, developing a total or totals for various indica and
storing data associated with a particular data processing form
and/or a group of data processing forms for further interpretation.
Photo-sensing equipment of this general type is disclosed by
sources such as, for example, U.S. Pat. Nos. 3,737,628 and
3,800,439.
FIG. 6 is an illustration of an exemplary photo-sensing apparatus
based on the transmitted-read method. A data processing form 40 has
a first or top surface 42 and a second or bottom surface 44. The
top surface 42 may have a sequence of timing marks 50 forming a
control mark column 52 (See FIG. 8). As best seen in FIG. 8,
associated with the control marks 50 are a plurality of
indicia-receiving locations 80 (e.g., response areas when the form
40 is used as a test answer sheet, a survey form, or the like). The
form 40 may have control marks 50 and indicia-receiving locations
80 on only one surface or on both surfaces. Thus, FIG. 6 shows
additional control marks 60 on the bottom surface 44. These are
shown as aligned with and symmetrically located relative to the
control marks 50 on the top surface, as may be required for
transmitted-read type forms.
An exemplary photo-sensing apparatus that may be used in a
transmitted-read method includes, as shown in FIG. 6, a light
source 20 adjacent the top surface 42 and a photo-sensor 30
adjacent the bottom surface 44. The photo-sensor 30 receives light
transmitted through the scannable form 40 which is made of a
suitable material that allows at least the minimum level of light
transmission to enable the transmitted-read equipment to function
properly when no indicia (e.g., mark) is present to occlude the
light. When an indicia is present, little or no light may reach the
photo-sensor 30. The electrical output of the photo-sensor 30 is
received by data processing means 32 and processed to discriminate
between indicia (e.g., mark) and "non-indicia" (e.g., non-mark).
(An exemplary scanner device using this scanning method is the
Sentry 3000 scanner sold by National Computer Systems, Inc., of
Eden Prairie, Minn. Other scanner devices using the
transmitted-read method may be available from other sources).
The indicia-receiving locations 80 are positioned on the form 40 to
have a particular orientation to the control marks 50. When the
photo-sensor 30 detects a control mark 50, it triggers the
photo-sensing apparatus to commence inspection for indicia which
may or may not be present in indicia-receiving locations 80
associated with the control mark 50. Additionally, data processing
forms that are processed by conventional transmitted-read methods
should avoid having any light-absorbing or light-blocking material
(e.g., marks, text, graphics, or the like) on the bottom surface 44
of the form that disrupt or interfere with light transmission
through the form from indicia-receiving locations 80 on the top
surface 42 (and vice versa, if the bottom surface 44 also has
indicia-receiving locations 80 that are to be processed).
FIG. 7 shows a photo-sensing apparatus based on the reflective-read
method. Equipment/systems of this type are disclosed by, for
example, U.S. Pat. Nos. 3,676,690 and 4,300,123. For purposes of
discussion, the data processing form 40 will be the same in both
FIG. 6 and FIG. 7. An exemplary photo-sensing apparatus that may be
used in the reflective-read method includes, as shown in FIG. 7, a
pair of light sources 120, 122 placed adjacent the top surface 42
of the data-processing form 40 so as to direct reflected light to a
photo-sensor 130 when indicia are absent from the indicia-receiving
location 80. When an indicia is present, little or no light may be
reflected to the photo-sensor 130. The electrical output of the
photo-sensor 130 is received by data processing means 132 and
processed in much the same manner as with transmitted-read
photo-sensor 30 to discriminate between indicia (e.g., mark) and
"non-indicia" (e.g., non-mark). To read both sides simultaneously,
a further light source-photosensor combination can be placed
adjacent the bottom surface 44 of the data processing form.
In view of the above, conventional photo-sensing apparatus, which
may incorporate computer software and/or hardware, may be
configured to inspect or "look" precisely at areas designated to
contain indicia and not at other areas in order to discriminate
between indicia (e.g., data marks), stray indicia (e.g., stray data
marks), non-indicia (e.g., material not intended to be detected by
photo-sensing apparatus), smudges, flaws in the document, or the
like. Moreover, data processing forms can have applications in
which only a few indicia-receiving locations are expected to
contain indicia. In those situations, photo-sensing apparatus are
designed or programmed to ignore indicia sensed in other areas. It
is very desirable for the data processing form to be as free of
clutter or markings which may interfere with the processing in
order to simplify the design of the photo-sensing apparatus and to
enhance the accuracy of processing the forms through the
photo-sensing apparatus.
For example, FIGS. 8 and 9 are illustrations of a portion of an
exemplary data processing form. This particular type of form
contains indicia-receiving locations that are darkened and
indicia-receiving locations that are filled in with alphanumeric
characters.
FIG. 8 illustrates a portion of a top surface 42 of an exemplary
data processing form 40. The data processing form 40 has
indicia-receiving locations 80 and other text 82 and graphics 84
defined by or formed from a mutable colored composition. The
mutable colored composition is the colored composition described
above and in the Examples. Some of the indicia-receiving locations
80 contain indicia 86. The top surface 42 of the data processing
form 40 is depicted in FIG. 8 prior to irradiating the colored
composition to irreversibly mutate the colorant.
The top surface 42 of the data processing form also contains
control marks 50 and other markings 52 that are printed with
conventional printing compositions (e.g., compositions containing
colorants or pigments that do not mutate, that is, they remain
detectable by the photo-sensing apparatus after being exposed to
conditions that would cause the colorant of the mutable colored
composition to irreversibly mutate).
FIG. 9 illustrates the exemplary data processing form shown in FIG.
8 after irradiating the colored composition to irreversibly mutate
the colorant. As depicted in FIG. 9, the colorant used to define
the indicia-receiving locations 80 and to form other text 82 and
graphics 84 has been irreversibly mutated and rendered
substantially undetectable (e.g., colorless or transparent),
leaving only the control marks 50 and the indicia 86.
Accordingly, the data processing forms of the present invention
provide an advantage in that any text, graphics, position markers
(e.g., marks defining indicia-receiving locations), or other
markings that should not be detected by the photo-sensing apparatus
can be eliminated or otherwise rendered undetectable prior to
processing the forms through the photo-sensing apparatus.
This objective may be accomplished with the data processing forms
of the present invention. In one embodiment, the form is composed
of: 1) a sheet of carrier material; and 2) a plurality of
indicia-receiving locations on at least a first surface of the
sheet. The indicia-receiving locations are defined by a colored
composition including a mutable colorant and an ultraviolet
radiation transorber. When the colored composition is irradiated
with ultraviolet radiation at a dosage level sufficient to
irreversibly mutate the colorant, the indicia-receiving locations
are adapted to become substantially undetectable by photo-sensing
apparatus. Desirably, the colored composition is irradiated with
radiation in the ultraviolet region of the electromagnetic spectrum
at a wavelength range between approximately 100 to 375
nanometers.
An embodiment of the method of practicing the method of the present
invention (i.e., improving the readability of a data processing
form used in photo-sensing apparatus that detect the presence of
indicia in indica-receiving locations on the form) is based on
utilizing data processing forms that have indicia-receiving
locations defined by the colored compositions described above and
in the Examples.
The steps of the method of the present invention are
straightforward and can be described as follows:
providing a data processing form that includes a sheet of carrier
material and indicia located at a plurality of indicia-receiving
locations on at least a first surface of the sheet, the
indicia-receiving locations being defined by a mutable colored
composition comprising a mutable colorant and an ultraviolet
radiation transorber,
irradiating the colored composition with ultraviolet radiation at a
dosage level sufficient to irreversibly mutable the colorant so
that the indicia-receiving locations are substantially undetectable
by photo-sensing apparatus, leaving the indicia to be detected.
Desirably, the colored composition is irradiated with radiation in
the ultraviolet region of the electromagnetic spectrum at a
wavelength of from about 100 to about 375 nanometers. As another
example, the ultraviolet radiation may be incoherent, pulsed
ultraviolet radiation from a dielectric barrier discharge excimer
lamp.
The data processing form may be irradiated individually as part of
a continuous irradiation step or the forms may be irradiated in
batches (after entry of the appropriate indicia at the
indicia-receiving locations) and then stored for any period of time
prior to being introduced into the photo-sensing apparatus.
Alternatively, the data processing forms may be irradiated as part
of a continuous process that includes a step of introducing the
forms into a photo-sensing apparatus.
Demonstrations of mutable colored compositions coated onto a
carrier material (which may be in the form of text, graphics and
indicia-receiving locations) and their subsequent irreversible
mutation by exposure to ultraviolet radiation are set forth in
Examples 1, 2, 3 and 4 below. Particular description of exemplary
electromagnetic radiation generating equipment that produces an
environment capable of irreversibly mutating the colored
composition described herein is set forth in Examples 10, 11 and 12
as well as the associated Figures.
The method of the present invention is adaptable to work with
transmitted-read data processing forms and/or reflective-read data
processing forms. It is contemplated that intermediate steps may be
incorporated into the method of the present invention. It is
further contemplated that other formats of data processing forms
may be used if it is desired that text, graphics, position markers
(e.g., marks defining indicia-receiving locations), or other
markings that should not be detected by the photo-sensing apparatus
are to be eliminated or otherwise render undetectable prior to
processing the forms through the photo-sensing apparatus.
Many data processing forms also have the limitations related to the
indicia intended to be detected by photo-sensing apparatus. If the
indicia is pre-printed prior to scanning, it is often very
difficult or even impossible to modify or erase the indicia prior
to processing. In many situations, it may be desirable to quickly
and efficiently erase or modify indicia that are to be detected by
photo-sensing apparatus. For example, data processing forms that
contain indicia (e.g., dots, shapes, alpha-numeric characters,
lines, bars or the like) in so many formats (e.g., coupons,
packaging labels, parts labels or tags, inventory labels or tags,
assembly-line work-in-progress labels or tags, baggage handling
labels or tags, medical labels or tags, checks, identification
cards, admission cards, admission tickets, credit cards, monetary
instruments, transportation tickets, bar code stickers, bills, or
the like) are used in such large numbers that the cost of
reprinting or replacing the indicia on each item simply to change
or alter the indicia could become significant. For example, FIGS.
10 and 11 are illustrations of a portion of an exemplary data
processing form. This particular type of form contains indicia in
the format of vertical bars intended to be detected or read by a
photo-sensing apparatus utilizing the reflective-read method.
FIG. 10 illustrates an exemplary data processing form 200 having a
only a portion of the indicia 220 formed from the mutable colored
composition described above and in the Examples prior to
irradiating the colored composition to irreversibly mutate the
colorant. The indicia 220 on data-processing form 200 shown in FIG.
10 is in the ubiquitous "bar code" format. indicia in such a format
typically is processed by laser "reflective-read" photo-sensing
apparatus.
FIG. 11 illustrates the same exemplary data processing form 200
after irradiating the colored composition to irreversibly mutate
the colorant. As is shown in the illustration, the colorant used to
form several of the indicia has been irreversibly mutated and
rendered substantially undetectable (e.g., colorless or
transparent), effecting the desired modification of the
indicia.
Accordingly, the data processing forms of the present invention
provide an advantage in that it is possible to modify or erase
indicia formed from the mutable colored composition in a
data-processing form without reprinting or replacing the indicia on
each item.
This objective can be accomplished by the data processing forms of
the present invention. An embodiment of the present invention
encompasses a data processing form that includes a plurality of
mutable indicia. At least a portion of the indicia are formed from
a mutable colored composition as described above and in the
Examples. The colored composition includes a mutable colorant and
an ultraviolet radiation transorber. When the colored composition
is irradiated with ultraviolet radiation at a dosage level
sufficient to irreversibly mutate the colorant, the indicia that
are formed from the colored composition are adapted to become
substantially undetectable by photo-sensing apparatus. Desirably,
the colored composition is irradiated with radiation in the
ultraviolet region of the ultraviolet spectrum. For example, the
colored composition may be irradiated with ultraviolet radiation at
a wavelength of from about 100 to about 375 nanometers. As another
example, the ultraviolet radiation may be incoherent, pulsed
ultraviolet radiation from a dielectric barrier discharge excimer
lamp.
The method of practicing an embodiment of the method of the present
invention (i.e., modifying indicia on a data processing form used
in photo-sensing apparatus that detect the presence of indicia at
indica-receiving locations on the form) is based on utilizing data
processing forms that have at least some indicia formed from the
colored compositions described above and in the Examples.
The steps of the method of the present invention are
straightforward and can be described as follows:
providing a data processing form that includes a sheet of carrier
material and a plurality of indicia at indicia-receiving locations
on at least a first surface of the sheet, at least a portion of the
indicia being mutable indicia formed from a colored composition
including a mutable colorant and an ultraviolet radiation
transorber;
irradiating the colored composition with ultraviolet radiation at a
dosage level sufficient to irreversibly mutate the colorant so that
at least a portion of the mutable indicia are substantially
undetectable by photo-sensing apparatus.
The data processing form may be irradiated individually as part of
a continuous irradiation step or the forms may be irradiated in
batches (after entry of the appropriate indicia in the
indicia-receiving locations) and then stored for any period of time
prior to being introduced into the photo-sensing apparatus.
Alternatively, the data processing forms may be irradiated as part
of a continuous process that includes a step of introducing the
forms into a photo-sensing apparatus.
Demonstrations of mutable colored compositions coated onto a
carrier material (which may be in the form of mutable indicia) and
their subsequent irreversible mutation by exposure to ultraviolet
radiation are set forth in Examples 1, 2, 3 and 4 below. Particular
description of exemplary electromagnetic radiation generating
equipment that produces an environment capable of irreversibly
mutating the colored composition described herein is set forth in
Examples 10, 11 and 12 as well as the associated Figures.
The method of the present invention is adaptable to work with
transmitted-read data processing forms and/or reflective-read data
processing forms. It is contemplated that intermediate steps may be
incorporated into the method of the present invention. It is
further contemplated that other formats of data processing forms
may be used if it is desired to modify or erase indicia from the
data processing forms prior to processing the forms through the
photo-sensing apparatus.
Aspects of the present invention are further described by the
examples that follow. Such examples, however, are not to be
construed as limiting in any way either the spirit or scope of the
present invention. In the examples, all parts are parts by weight
unless stated otherwise.
EXAMPLE 1
This example describes the preparation of films consisting of
colorant, ultraviolet radiation transorber, and thermoplastic
polymer. The colorant and ultraviolet radiation transorber were
ground separately in a mortar. The desired amounts of the ground
components were weighed and placed in an aluminum pan, along with a
weighed amount of a thermoplastic polymer. The pan was placed on a
hot plate set at 150.degree. C. and the mixture in the pan was
stirred until molten. A few drops of the molten mixture were poured
onto a steel plate and spread into a thin film by means of a glass
microscope slide. Each steel plate was 3.times.5 inches (7.6
cm.times.12.7 cm) and was obtained from Q-Panel Company, Cleveland,
Ohio. The film on the steel plate was estimated to have a thickness
of the order of 10-20 micrometers.
In every instance, the colorant was Malachite Green oxalate
(Aldrich Chemical Company, Inc., Milwaukee, Wis.), referred to
hereinafter as Colorant A for convenience. The ultraviolet
radiation transorber ("UVRT") consisted of one or more of
Irgacure.RTM. 500 ("UVRT A"), Irgacure.RTM. 651 ("UVRT B"), and
Irgacure.RTM. 907 ("UVRT C"), each of which was described earlier
and is available from Ciba-Geigy Corporation, Hawthorne, N.Y. The
polymer was one of the following: an epichlorohydrin-bisphenol A
epoxy resin ("Polymer A"), Epon.RTM. 1004F (Shell Oil Company,
Houston, Tex.); a poly(ethylene glycol) having a weight-average
molecular weight of about 8,000 ("Polymer B"), Carbowax 8000
(Aldrich Chemical Company); and a poly(ethylene glycol) having a
weight-average molecular weight of about 4,600 ("Polymer C"),
Carbowax 4600 (Aldrich Chemical Company). A control film was
prepared which consisted only of colorant and polymer. The
compositions of the films are summarized in Table 1.
TABLE 1 ______________________________________ Compositions of
Films Containing Colorant and Ultraviolet Radiation Transorber
("UVRT") Colorant UVRT Polymer Film Type Parts Type Parts Type
Parts ______________________________________ A A 1 A 6 A 90 C 4 B A
1 A 12 A 90 C 8 C A 1 A 18 A 90 C 12 D A 1 A 6 A 90 B 4 E A 1 B 30
A 70 F A 1 -- -- A 100 G A 1 A 6 B 90 C 4 H A 1 B 10 C 90
______________________________________
While still on the steel plate, each film was exposed to
ultraviolet radiation. In each case, the steel plate having the
film sample on its surface was placed on a moving conveyor belt
having a variable speed control. Three different ultraviolet
radiation sources, or lamps, were used. Lamp A was a 222-nanometer
excimer lamp and Lamp B was a 308-nanometer excimer lamp, as
already described. Lamp C was a fusion lamp system having a "D"
bulb (Fusion Systems Corporation, Rockville, Md.). The excimer
lamps were organized in banks of four cylindrical lamps having a
length of about 30 cm, with the lamps being oriented normal to the
direction of motion of the belt. The lamps were cooled by
circulating water through a centrally located or inner tube of the
lamp and, as a consequence, they operated at a relatively low
temperature, i.e., about 50.degree. C. The power density at the
lamp's outer surface typically is in the range of from about 4 to
about 20 joules per square meter (J/m.sup.2).
However, such range in reality merely reflects the capabilities of
current excimer lamp power supplies; in the future, higher power
densities may be practical. With Lamps A and B, the distance from
the lamp to the film sample was 4.5 cm and the belt was set to move
at 20 ft/min (0.1 m/sec). With Lamp C, the belt speed was 14 ft/min
(0.07 m/sec) and the lamp-to-sample distance was 10 cm. The results
of exposing the film samples to ultraviolet radiation are
summarized in Table 2. Except for Film F, the table records the
number of passes under a lamp which were required in order to
render the film colorless. For Film F, the table records the number
of passes tried, with the film in each case remaining colored (no
change).
TABLE 2 ______________________________________ Results of Exposing
Films Containing Colorant and Ultraviolet Radiation Transorber
(UVRT) to Ultraviolet Radiation Excimer Lamp Film Lamp A Lamp B
Fusion Lamp ______________________________________ A 3 3 15 B 2 3
10 C 1 3 10 D 1 1 10 E 1 1 1 F 5 5 10 G 3 -- 10 H 3 -- 10
______________________________________
EXAMPLE 2
This example describes the preparation of solid colored
compositions adapted to be utilized as toners in an
electrophotographic process. In every instance, the toner included
Colorant A as described in Example 1; a polymer, DER 667, an
epichlorohydrin-bisphenol A epoxy resin (Polymer D), Epon.RTM.
1004F (Dow Chemical Company, Midland, Mich.); and a charge control
agent, Carrier A, which consisted of a very finely divided
polymer-coated metal. The ultraviolet radiation transorber (UYRT)
consisted of one or more of UVRT B from Example 1, Irgacure.RTM.
369 (UVRT D), and Irgacure.RTM. 184 (UVRT E); the latter two
transorbers were described earlier and are available from
Ciba-Geigy Corporation, Hawthorne, N.Y. In one case, a second
polymer also was present, styrene acrylate 1221, a styrene-acrylic
acid copolymer (Hercules Incorporated, Wilmington, Del.).
To prepare the toner, colorant, ultraviolet radiation transorber,
and polymer were melt-blended in a Model 3VV 800E, 3 inch.times.7
inch (7.6 cm.times.17.8 cm) two-roll research mill (Farrel
Corporation, Ansonia, Conn.). The resulting melt-blend was powdered
in a Mikropul hammermill with a 0.010-inch herringbone screen (R.
D. Kleinfeldt, Cincinnati, Ohio) and then sieved for proper
particle sizes in a Sturtvant, air two-inch micronizer (R. D.
Kleinfeldt) to give what is referred to herein as a pretoner.
Charge control agent then was added to the pretoner and the
resulting mixture blended thoroughly. Table 3 summarizes the
compositions of the pretoners and Table 4 summarizes the
compositions of the toners.
TABLE 3 ______________________________________ Summary of Pretoner
Compositions Colorant UVRT Polymer Pretoner A (g) Type g Type g
______________________________________ A 1 D 20 D 80 B 1 B 20 D 80
C 1 B 10 D 80 D 10 D 1 B 6.9 D 40 D 6.6 E 40 E 6.6
______________________________________
TABLE 4 ______________________________________ Summary of Toner
Compositions Pretoner Charge Toner Type g Control Agent (g)
______________________________________ A A 8.4 210 B B 8.4 210 C C
8.4 210 D D 8.4 210 ______________________________________
Each toner was placed separately in a Sharp Model ZT-50TD1 toner
cartridge and installed in either a Sharp Model Z-76 or a Sharp
Model Z-77 xerographic copier (Sharp Electronics Corporation,
Mahwah, N.J.). Images were made in the usual manner on bond paper
(Neenah Bond). The image-bearing sheets then were exposed to
ultraviolet radiation from Lamp B as described in Example 1. In
each case, the image was rendered colorless with one pass.
EXAMPLE 3
This example describes the preparation of a .beta.-cyclodextrin
molecular includant having (1) an ultraviolet radiation transorber
covalently bonded to the cyclodextrin outside of the cavity of the
cyclodextrin and (2) a colorant associated with the cyclodextrin by
means of hydrogen bonds and/or van der Waals forces.
A. Friedel-Crafts Acylation of Transorber
A 250-ml, three-necked, round-bottomed reaction flask was fitted
with a condenser and a pressure-equalizing addition funnel equipped
with a nitrogen inlet tube. A magnetic stirring bar was placed in
the flask. While being flushed with nitrogen, the flask was charged
with 10 g (0.05 mole) of 1-hydroxycyclohexyl phenyl ketone
(Irgacure.RTM. 184, Ciba-Geigy Corporation, Hawthorne, N.Y.), 100
ml of anhydrous tetrahydofuran (Aldrich Chemical Company, Inc.,
Milwaukee, Wis.), and 5 g (0.05 mole) of succinic anhydride
(Aldrich). To the continuously stirred contents of the flask then
was added 6.7 g of anhydrous aluminum chloride (Aldrich). The
resulting reaction mixture was maintained at about 0.degree. C. in
an ice bath for about one hour, after which the mixture was allowed
to warm to ambient temperature for two hours. The reaction mixture
then was poured into a mixture of 500 ml of ice water and 100 ml of
diethyl ether. The ether layer was removed after the addition of a
small amount of sodium chloride to the aqueous phase to aid phase
separation. The ether layer was dried over anhydrous magnesium
sulfate. The ether was removed under reduced pressure, leaving 12.7
g (87 percent) of a white crystalline powder. The material was
shown to be 1-hydroxycyclohexyl 4-(2-carboxyethyl)carbonylphenyl
ketone by nuclear magnetic resonance analysis.
B. Preparation of Acylated Transorber Acid Chloride
A 250-ml round-bottomed flask fitted with a condenser was charged
with 12.0 g of 1-hydroxycyclohexyl 4-(2-carboxyethyl)carbonylphenyl
ketone (0.04 mole), 5.95 g (0.05 mole) of thionyl chloride
(Aldrich), and 50 ml of diethyl ether. The resulting reaction
mixture was stirred at 30.degree. C. for 30 minutes, after which
time the solvent was removed under reduced pressure. The residue, a
white solid, was maintained at 0.01 Torr =30 minutes to remove
residual solvent and excess thionyl chloride, leaving 12.1 g (94
percent) of 1-hydroxycyclohexyl
4-(2-chloroformylethyl)carbonylphenyl ketone.
C. Covalent Bonding of Acylated Transorber to Cyclodextrin
A 250-ml, three-necked, round-bottomed reaction flask containing a
magnetic stirring bar and fitted with a thermometer, condenser, and
pressure-equalizing addition funnel equipped with a nitrogen inlet
tube was charged with 10 g (8.8 mmole) of .beta.-cyclodextrin
(American Maize-Products Company, Hammond, Ind.), 31.6 g (98 mmole
s) of 1-hydroxycyclohexyl 4-(2-chloroformylethyl)carbonylphenyl
ketone, and 100 ml of N,N-dimethylformamide while being
continuously flushed with nitrogen. The reaction mixture was heated
to 50.degree. C. and 0.5 ml of triethyl amine added. The reaction
mixture was maintained at 50.degree. C. for an hour and allowed to
cool to ambient temperature. In this preparation, no attempt was
made to isolate the product, a .beta.-cyclodextrin to which an
ultraviolet radiation transorber had been covalently coupled
(referred to hereinafter for convenience as
-cyclodextrin-transorber).
The foregoing procedure was repeated to isolate the product of the
reaction. At the conclusion of the procedure as described, the
reaction mixture was concentrated in a rotary evaporator to roughly
10 percent of the original volume. The residue was poured into ice
water to which sodium chloride then was added to force the product
out of solution. The resulting precipitate was isolated by
filtration and washed with diethyl ether. The solid was dried under
reduced pressure to give 24.8 g of a white powder. In a third
preparation, the residue remaining in the rotary evaporator was
placed on top of an approximately 7.5-cm column containing about 15
g of silica gel. The residue was eluted with N,N-dimethylformamide,
with the eluant being monitored by means of Whatman.RTM.
Flexible-Backed TLC Plates (Catalog No. 05-713-161, Fisher
Scientific, Pittsburgh, Pa.). The eluted product was isolated by
evaporating the solvent. The structure of the product was verified
by nuclear magnetic resonance analysis.
D. Association of Colorant with Cyclodextrin-Transorber-Preparation
of Colored Composition
To a solution of 10 g (estimated to be about 3.6 mmole) of
beta-cyclodextrin-transorber in 150 ml of N,N-dimethylformamide in
a 250-ml round-bottomed flask was added at ambient temperature 1.2
g (3.6 mmole) of Malachite Green oxalate (Aldrich Chemical Company,
Inc., Milwaukee, Wis.), referred to hereinafter as Colorant A for
convenience. The reaction mixture was stirred with a magnetic
stirring bar for one hour at ambient temperature. Most of the
solvent then was removed in a rotary evaporator and the residue was
eluted from a silica gel column as already described. The
beta-cyclodextrin-transorber Colorant A inclusion complex moved
down the column first, cleanly separating from both free Colorant A
and beta-cyclodextrin-transorber. The eluant containing the complex
was collected and the solvent removed in a rotary evaporator. The
residue was subjected to a reduced pressure of 0.01 Torr to remove
residual solvent to yield a blue-green powder.
E. Mutation of Colored Composition
The beta-cyclodextrin-transorber Colorant A inclusion complex was
exposed to ultraviolet radiation from two different lamps, Lamps A
and B. Lamp A was a 222-nanometer excimer lamp assembly organized
in banks of four cylindrical lamps having a length of about 30 cm.
The lamps were cooled by circulating water through a centrally
located or inner tube of the lamp and, as a consequence, they
operated at a relatively low temperature, i.e., about 50.degree. C.
The power density at the lamp's outer surface typically is in the
range of from about 4 to about 20 joules per square meter
(J/m.sup.2). However, such range in reality merely reflects the
capabilities of current excimer lamp power supplies; in the future,
higher power densities may be practical. The distance from the lamp
to the sample being irradiated was 4.5 cm. Lamp B was a 500-watt
Hanovia medium pressure mercury lamp (Hanovia Lamp Co., Newark,
N.J.). The distance from Lamp B to the sample being irradiated was
about 15 cm.
A few drops of an N,N-dimethylformamide solution of the
beta-cyclodextrin-transorber Colorant A inclusion complex were
placed on a TLC plate and in a small polyethylene weighing pan.
Both samples were exposed to Lamp A and were decolorized (mutated
to a colorless state) in 15-20 seconds. Similar results were
obtained with Lamp B in 30 seconds.
A first control sample consisting of a solution of Colorant A and
beta-cyclodextrin in N,N-dimethylformamide was not decolorized by
Lamp A. A second control sample consisting of Colorant A and
1-hydroxycyclohexyl phenyl ketone in N,N-dimethylformamide was
decolorized by Lamp A within 60 seconds. On standing, however, the
color began to reappear within an hour.
To evaluate the effect of solvent on decolorization, 50 mg of the
beta-cyclodextrin-transorber Colorant A inclusion complex was
dissolved in 1 ml of solvent. The resulting solution or mixture was
placed on a glass microscope slide and exposed to Lamp A for 1
minute. The rate of decolorization, i.e., the time to render the
sample colorless, was directly proportional to the solubility of
the complex in the solvent, as summarized below.
______________________________________ Decolorization Solvent
Solubility Time ______________________________________
N,N-Dimethylformamide Poor 1 minute Dimethylsulfoxide Soluble
<10 seconds Acetone Soluble <10 seconds Hexane Insoluble --
Ethyl Acetate Poor 1 minute
______________________________________
Finally, 10 mg of the beta-cyclodextrin-transorber Colorant A
inclusion complex were placed on a glass microscope slide and
crushed with a pestle. The resulting powder was exposed to Lamp A
for 10 seconds. The powder turned colorless. Similar results were
obtained with lamp B, but at a slower rate.
EXAMPLE 4
Because of the possibility in the preparation of colored
composition described in Example 3 for the acytated transorber acid
chloride to at least partially occupy the cavity of the
cyclodextrin, to the partial or complete exclusion of colorant, a
modified preparative procedure was carried out. Thus, this example
describes the preparation of a beta-cyclodextrin molecular
includant having (1) a colorant at least partially included within
the cavity of the cyclodextrin and associated therewith by means of
hydrogen bonds and/or van der Waals forces and (2) an ultraviolet
radiation transorber covalently bonded to the cyclodextrin outside
of the cavity of the cyclodextrin.
A. Association of Colorant with a Cyclodextrin
To a solution of 10.0 g (8.8 mmole ) of beta-cyclodextrin in 150 ml
of N,N-dimethylformamide was added 3.24 g (9.6 mmoles) of Colorant
A. The resulting solution was stirred at ambient temperature for
one hour. The reaction solution was concentrated under reduced
pressure in a rotary evaporator to a volume about one-tenth of the
original volume. The residue was passed over a silica gel column as
described in Part C of Example 1. The solvent in the eluant was
removed under reduced pressure in a rotary evaporator to give 12.4
g of a blue-green powder, beta-cyclodextrin Colorant A inclusion
complex.
B. Covalent Bonding of Acylated Transorber to Cyclodextrin Colorant
inclusion Complex-Preparation of Colored Composition
A 250-ml, three-necked, round-bottomed reaction flask containing a
magnetic stirring bar and fitted with a thermometer, condenser, and
pressure-equalizing addition funnel equipped with a nitrogen inlet
tube was charged with 10 g (9.6 mmole) of beta-cyclodextrin
Colorant A inclusion complex, 31.6 g (98 mmoles) of
1-hydroxycyclohexyl 4-(2-chloroformylethyl)carbonylphenyl ketone
prepared as described in Part B of Example 1, and 150 ml of
N,N-dimethylformamide while being continuously flushed with
nitrogen. The reaction mixture was heated to 50.degree. C. and 0.5
ml of triethylamine added. The reaction mixture was maintained at
50.degree. C. for an hour and allowed to cool to ambient
temperature. The reaction mixture then was worked up as described
in Part A, above, to give 14.2 g of beta-cyclodextrin-transorber
Colorant A inclusion complex, a blue-green powder.
C. Mutation of Colored Composition
The procedures described in Part E of Example 1 were repeated with
the beta-cyclodextrin-transorber Colorant A inclusion complex
prepared in part B, above, with essentially the same results.
EXAMPLE 5
This Example describes a method of preparing an ultraviolet
radiation transorber designated phthaloylglycine-2959.
The following was admixed in a 250 ml 3-necked round bottomed flask
fitted with a Dean & Stark adapter with condenser and two glass
stoppers: 20.5 g (0.1 mole) of the wavelength selective sensitizer,
phthaloylglycine (Aldrich); 24.6 g (0.1 mole ) of the photoreactor,
DARCUR 2959 (Ciba-Geigy, Hawthorne, NY); 100 ml of benzene
(Aldrich); and 0.4 g p-toluene sulfonic acid (Aldrich). The mixture
was heated at reflux for 3 hours after which time 1.8 ml of water
was collected. The solvent was removed under reduced pressure to
give 43.1 g of white powder. The powder was recrystallized from 30%
ethyl acetate in hexane (Fisher) to yield 40.2 g (93%) of a white
crystalline powder having a melting point of 153.degree.-4.degree.
C. The resulting product, designated phthaloyl glycine-2959, had
the following physical parameters:
IR [Nujol Mull]] .nu..sub.max 3440, 1760, 1740, 1680, 1600
cm.sup.-1
.sup.1 HNMR [CDCL.sub.3 ] .differential. ppm 1.64[s], 4.25[m],
4.49[m], 6.92[m], 7.25[m], 7.86[m], 7.98[m], 8.06[m] ppm
EXAMPLE 6
This Example describes a method of dehydrating the
phthaloylglycine-2959 produced in Example 5.
The following was admixed in a 250 ml round bottomed flask fitted
with a Dean & Stark adaptor with condenser: 21.6 g (0.05 mole)
phthaloylglycine-2959; 100 ml of anhydrous benzene (Aldrich); and
0.1 g p-toulene sulfonic acid (Aldrich). The mixture was refluxed
for 3 hours. After 0.7 ml of water had been collected in the trap,
the solution was then removed under vacuum to yield 20.1 g (97%) of
a white solid. The solid was used without further purification.
The resulting reaction product had the following physical
parameters:
IR (NUJOL) .nu..sub.max 1617 cm.sup.-1 (C.dbd.C--C.dbd.O)
EXAMPLE 7
This Example describes a method of producing a beta-cyclodextrin
having dehydrated phthaloylglycine-2959 groups from Example 6
covalently bonded thereto.
The following was admixed in a 100 ml round bottomed Flask: 5.0 g
(4.4 mmole) beta-cyclodextrin (American Maize Product Company,
Hammond, Ind.) (designated beta-CD in the following reaction); 8.3
g (20 mmole) dehydrated phthaloylglycine-2959; 50 ml of anhydrous
DMF; 20 ml of benzene; and 0.01 g p-tolulenesulfonyl chloride
(Aldrich). The mixture was chilled in a salt/ice bath and stirred
for 24 hours. The reaction mixture was poured into 150 ml of weak
sodium bicarbonate solution and extracted three times with 50 ml
ethyl ether. The aqueous layer was then filtered to yield a whine
solid comprising the beta-cyclodextrin with phthaloylglycine-2959
group attached. A yield of 9.4 g was obtained. Reverse phase TLC
plate using a 50:50 DMF:acetonitrile mixture showed a new product
peak compared to the starting materials.
Of course, the beta-cyclodextrin molecule has several primary
alcohols and secondary alcohols with which the
phthaloylglycine-2959 can react.
EXAMPLE 8
This example describes a method of associating a colorant and an
ultraviolet radiation transorber with a molecular includant. More
particularly, this Example describes a method of associating the
colorant crystal violet with the molecular includant
beta-cyclodextrin covalently bonded to the ultraviolet radiation
transorber phthaloylglycine-2959 of Example 7.
The following was placed in a 100 ml beaker: 4.0 g
beta-cyclodextrin having a dehydrated phthaloylglycine-2959 group;
and 50 ml of water. The water was heated to 70.degree. C. at which
point the solution became clear. Next, 0.9 g (2.4 mmole) crystal
violet (Aldrich Chemical Company, Milwaukee, Wis.) was added to the
solution, and the solution was stirred for 20 minutes. Next, the
solution was then filtered. The filtrand was washed with the
filtrate and then dried in a vacuum oven at 84.degree. C. A
violet-blue powder was obtained having 4.1 g (92%) yield. The
resulting reaction product had the following physical
parameters:
U.V. Spectrum DMF .LAMBDA..sub.max 610 nm (cf cv .LAMBDA..sub.max
604 nm)
EXAMPLE 9
This Example describes a method of producing the ultraviolet
radiation transorber 4(4-hydroxyphenyl) butan-2-one-2959 (chloro
substituted).
The following was admixed in a 250 ml round bottomed flask fitted
with a condenser and magnetic stir bar: 17.6 g (0.1 mole) of the
wavelength selective sensitizer, 4(4-hydroxyphenyl) butan-2-one
(Aldrich Chemical Company, Milwaukee, Wis.); 26.4 g (0.1 mole) of
the photoreactor, chloro substituted DARCUR 2959 (Ciba-Geigy
Corporation, Hawthorne, N.Y.); 1.0 ml of pyridine (Aldrich Chemical
Company, Milwaukee, Wis.); and 100 ml of anhydrous tetrahydrofuran
(Aldrich Chemical Company, Milwaukee, Wis.). The mixture was
refluxed for 3 hours and the solvent partially removed under
reduced pressure (60% taken off). The reaction mixture was then
poured into ice water and extracted with two 50 ml aliquots of
diethyl ether. After drying over anhydrous magnesium sulfate and
removal of solvent, 39.1 g of white solvent remained.
Recrystallization of the powder from 30% ethyl acetate in hexane
gave 36.7 g (91%) of a white crystalline powder, having a melting
point of 142.degree.-3.degree. C.
The resulting reaction product had the following physical
parameters:
IR [Nujol Mull] .nu..sub.wax 3460, 1760, 1700, 1620, 1600
cm.sup.-1
.sup.1 H [CDCL.sub.3 ] .differential. ppm 1.62[s], 4.2[m], 4.5[m],
6.9[m] ppm
The ultraviolet radiation transorber produced in this Example
4(4-hydroxyphenyl) butan-2-one-2959 (chloro substituted), may be
associated with beta-cyclodextrin and a colorant such as crystal
violet, using the methods described above in Examples 6 through 8
wherein 4(4-hydroxyphenyl) butan-2-one-2959 (chloro substituted)
would be substituted for the dehydrated phthaloylglycine-2959 in
the methods in Examples 6 through 8.
EXAMPLE 10
This Example demonstrates that the 222 nanometer excimer lamps
illustrated in FIG. 3 produce uniform intensity readings on a
surface of a substrate 5.5 centimeters from the lamps, at the
numbered locations, in an amount sufficient to mutate the colorant
in the compositions of the present invention which are present on
the surface of the substrate. The lamp 10 comprises a lamp housing
15 with four excimer lamp bulbs 20 positioned in parallel, the
excimer lamp bulbs 20 are approximately 30 cm in length. The lamps
are cooled by circulating water through a centrally located or
inner tube (not shown) and, as a consequence, the lamps are
operated at a relatively low temperature, i.e., about 50.degree. C.
The power density at the lamp's outer surface typically is in the
range of from about 4 to about 20 joules per square meter
(J/m.sup.2).
Table 5 summarizes the intensity readings which were obtained by a
meter located on the surface of the substrate. The readings
numbered 1, 4, 7, and 10 were located approximately 7.0 centimeters
from the left end of the column as shown in FIG. 3. The readings
numbered 3, 6, 9, and 12 were located approximately 5.5 centimeters
from the right end of the column as shown in FIG. 3. The readings
numbered 2, 5, 8, and 11 were centrally located approximately 17.5
centimeters from each end of the column as shown in FIG. 3.
TABLE 5 ______________________________________ Background (.mu.W)
Reading (mW/cm.sup.2) ______________________________________ 24.57
9.63 19.56 9.35 22.67 9.39 19.62 9.33 17.90 9.30 19.60 9.30 21.41
9.32 17.91 9.30 23.49 9.30 19.15 9.36 17.12 9.35 21.44 9.37
______________________________________
EXAMPLE 11
This Example demonstrates that the 222 nanometer excimer lamps
illustrated in FIG. 4 produce uniform intensity readings on a
surface of a substrate 5.5 centimeters from the lamps, at the
numbered locations, in an amount sufficient to mutate the colorant
in the compositions of the present invention which are present on
the surface of the substrate. The excimer lamp 10 comprises a lamp
housing 15 with four excimer lamp bulbs 20 positioned in parallel,
the excimer lamp bulbs 20 are approximately 30 cm in length. The
lamps are cooled by circulating water through a centrally located
or inner tube (not shown) and, as a consequence, the lamps are
operated at a relatively low temperature, i.e., about 50.degree. C.
The power density at the lamp's outer surface typically is in the
range of from about 4 to about 20 joules per square meter
(J/m.sup.2).
Table 6 summarizes the intensity readings which were obtained by a
meter located on the surface of the substrate. The readings
numbered 1, 4, and 7 were located approximately 7.0 centimeters
from the left end of the columns as shown in FIG. 4. The readings
numbered 3, 6, and 9 were located approximately 5.5 centimeters
from the right end of the columns as shown in FIG. 4. The readings
numbered 2, 5, 8 were centrally located approximately 17.5
centimeters from each end of the columns as shown in FIG. 4.
TABLE 6 ______________________________________ Background (.mu.W)
Reading (mW/cm.sup.2) ______________________________________ 23.46
9.32 16.12 9.31 17.39 9.32 20.19 9.31 16.45 9.29 20.42 9.31 18.33
9.32 15.50 9.30 20.90 9.34
______________________________________
EXAMPLE 12
This Example demonstrates the intensity produced by the 222
nanometer excimer lamps illustrated in FIG. 5, on a surface of a
substrate, as a function of the distance of the surface from the
lamps, the intensity being sufficient to mutate the colorant in the
compositions of the present invention which are present on the
surface of the substrate. The excimer lamp 10 comprises a lamp
housing 15 with four excimer lamp bulbs 20 positioned in parallel,
the excimer lamp bulbs 20 are approximately 30 cm in length. The
lamps are cooled by circulating water through a centrally located
or inner tube (not shown) and, as a consequence, the lamps are
operated at a relatively low temperature, i.e., about 50.degree. C.
The power density at the lamps outer surface typically is in the
range of from about 4 to about 20 joules per square meter
(J/m.sup.2).
Table 7 summarizes the intensity readings which were obtained by a
meter located on the surface of the substrate at position t as
shown in FIG. 5. Position 1 was centrally located approximately 17
centimeters from each end of the column as shown in FIG. 5.
TABLE 7 ______________________________________ Distance (cm)
Background (.mu.W) Reading(mW/cm.sup.2)
______________________________________ 5.5 18.85 9.30 6.0 15.78
9.32 10 18.60 9.32 15 20.90 9.38 20 21.67 9.48 25 19.86 9.69 30
22.50 11.14 35 26.28 9.10 40 24.71 7.58 50 26.95 5.20
______________________________________
Having thus described the invention, numerous changes and
modifications hereof will be readily apparent to those having
ordinary skill in the art without departing from the spirit or
scope of the invention.
* * * * *